Certain oximinophosphonodithioates as insecticides and acaricides

ABSTRACT

COMPOUNDS HAVING THE FORMULA   IN WHICH R IS ALKYL, R1 IS HYDROGEN, NITRO, OR HALOGEN, R2 IS ALKYL, AND R3 IS ((1) HYDROGEN, (2) LOWER ALKYLTHIO, (3) CYANO, (4) ALKYL, AND (5) ETHYNYL AND THEIR USE AS INSECTICIDES AND ACRICIDES.   R1-C6H4-C(-R)=N-O-P(=S)(-R2)-S-CH2-R3

United States Patent 3,737,530 CERTAIN OXTMINOPHOSPHONODITHIOATES AS INSECTICIDES AND ACARICIDES Arnold D. Gutman, Berkeley, Calif., assignor to Stautfer Chemical Company, New York, N.Y. No Drawing. Original application Apr. 6, 1970, Ser. No. 26,151, now Patent No. 3,709,959, dated Jan. 9, 1973. Divided and this application June 12, 1972, Ser. No.

Int. Cl. A0111 9/36 U.S. Cl. 424-210 10 Claims This is a division of application Ser. No. 26,151 filed Apr. 6, 1970, now US. Pat. 3,709,959 issued Jan. 9, 1973.

This invention relates to certain novel chemical compounds and their use as insecticides and acaricides. More particularly, the chemical compounds are certain oximinophosphonodithioates.

The compounds of this invention are those having the formula R s s CHr-R 1 I! in which R is alkyl having 1 to 4 carbon atoms, preferably branched chained, most preferably methyl; R is hydrogen, nitro, or halogen, preferably chlorine; R is alkyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and R is (1) hydrogen; (2) lower alkylthio having 1 to 2 carbon atoms; (3) cyano; (4) alkyl having 1 to 5 carbon atoms, (5) ethynyl.

The compounds of the present invention can be prepared according to the following reactions in which R, R R and R are as defined.

In the event that the desiredcompound cannot be prepared because of difficulty of preparing or obtainingthe compound nscn n r reaction 1 (b), then the following ice S SE ll/ XCHzR R S SCHzR in which R, R R and R are as defined and is chlorine, bromine, or iodine.

Preferably, reaction I(a) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any desired manner, but preferably, the reaction is run in a solvent such as THF by first preparing the salt of the oxime reactant with an acid acceptor such as potassium-t-butoxide at room temperature and then preferably, slowly adding the dichloride reactant thereto, preferably in solution with a solvent, for example, THF, at a temperature below about 15 C. for control. However, the oxime reactant can be used in place of the salt, preferably in the presence of the acid acceptor. The resulting product is recovered and purified by standard procedure. For example, the resulting product can be recovered from the reaction mixture and purified from the reaction mixture by adding the mixture to a non-polar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOH solution and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO, to yield the purified product.

Reaction I(b) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any manner but preferably the phosphorus containing reactant is slowly added to the reactant containing the -SH group in a solvent such as THF, preferably with stirring. More preferably, an alkali metal salt of this reactant is used to reduce the chance of a violent reaction. The temperature of the reaction is not critical, however, better yields are obtained by heating the reactants at reflux for a time sufficient to allow completion of the reaction. The resulting product can be recovered from the reaction mixture by adding the mixture to a non-polar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOH solution and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO to yield the purified product. The process represented by reaction II(a) is carried out by merely reacting the two reactants. Preferably, about 2 moles of the oxime reactant per mole thiono phosphine sulfide reactant should be used. If an excess of either reactant is used, the reaction still proceeds but yields are lowered. The reactants can be combined in any desired mariner. The reaction readily proceeds at room temperature and preferably is run under anhydrous conditions in a common solvent for the reactants such as benzene. The dithiophosphonic acid product can be recovered from its solvents in pure form, but it is preferred to not do so. If prolonged storage of the compound is desired, it is preferable to prepare either the alkali, alkaline or heavy metal salt of the acid.

Reaction II(b) utilizes as a reactantthe product of reaction II(a) preferably as a solution in the solvent utilized for reaction II(a). In this process, the reaction is carried out by reacting preferably about equal mole amounts of the reactants. If an excess of either reactant is used, the reaction still proceeds, but again yields are lowered. Although the reactants can be combined in any desired manner, it is preferred to add the halide reactant to a solution of the dithiophosphonic acid reactant, preferably the acid is not recovered from the solvent in which it is prepared. Preferably, the reaction is carried out at below room temperature about 1020 C. for control and in the presence of a base, such as triethylamine, to take up the liberated acid halide reaction product. The reaction product is recovered by conventional means such as described for reaction I(b).

Preparation of the compounds of this invention is illustrated in the following examples:

EXAMPLE I O-(4-chloro-acetophenoneoximino), ethyl-S-(methyl thioethyD-phosphono dithioate on. s SCHzSCHzCHa o=N o1- 01E 12.4 gms. (0.05 moles) of ethylthionophosphine sulfide, 17 gms. (0.102 moles) of 4-chloroacetophenoneoxime and 200 ml. of dioxane are combined in a l l. beaker and stirred magnetically at room temperature until a solution is obtained. The solution is stirred and cooled to C. in an ice bath. 11.1 gms. (0.1 moles) of chloro methyl ethylsulfide is added, followed by 15.1 gms. (0.15 moles) of triethylaimine added over a period of 10 minutes. The resulting mixture is stirred at room temperature for 1 hour, then poured into 500 ml. of benzene and consecutively, washed with 200 ml. of water, 100 ml. of saturated sodium bicarbonate solution, and 2 100 ml. portions of Water. The benzene phase is dried with anhydrous MgSO and evaporated to yield 28 gms. (72.5% of theory) of the desired product. N =l.6203.

The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

TABLE I R\ S S CHzR R C=N O P Compound number R R R R N n 1 CH3 H C2115 SCH l. 6107 2 CH3 H C2115 0 -CN 5774 3 CH3 E 02115 -SCH(CH3): 1 5913 4. CH3 l-NOa C2115 H 1. 6090 5.. CH3 4-N02 C2H5 --C=CH 1. 5987 6.-.. CH3 4-N0: C2115 --CN 5940 7 CH3 4-NO2 02115 SCH3 1. 6192 8 CH3 l NO: C2115 S CgHs 1. 6164 9 CH3 4-01 02H: -ON 1. 5868 10 CH3 4-01 CgHu C=CH 1 6043 11 CH3 4-01 CzHs -SCH3 1. 6217 12) CH3 4-01 CzHs SC:H5 1.6203

Prepared in Example I.

The following tests illustrate the insecticidal and acaricidal activity of the compounds of this invention. INSECTICIDAL EVALUATION TESTS The following insect species were used in evaluation tests for insecticidal activity:

(1) Housefly (HF)Mul$cw domestica (Linn.)

4 r (2) German (GR)--Blatella (Linn.)

(3) S'alt-marsch Caterpillar (SMC)Estigmene acrea (Drury) 1(4) Ly-gus Bug '(LB)Lygus hesperus (Knight (5) Bean Aphid (BA)-Aphis fabae (Scop.)

The Housefly (HF) was used in evaluation tests of selected compounds as insecticides by the following procedure. A stock solution containing ug/ml. of the toxicant in an appropriate solvent was prepared. Aliquots of this solution were combined with 1 milliliter of an acetone-peanut oil solution in an aluminum dish and allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100 g. per dish to that at which 50% mortality was attained. The dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female houseflies, three to five days old, were introduced into the cage and the percent mortality was recorded after 48 hours. The LD-SO values are expressed in terms of ,ug. per 25 female flies. The results of these insecticidal evaluation tests are given in Table II under In the German Cockroach (GR) tests, 10 one-month old nymphs were placed in separate circular cardboard cages sealed on one end with cellophane and covered by a cloth netting on the other. Aliquots of the toxicants, dissolved in an appropriate solvent, were diluted in water containing 0.002% of a wetting agent, Sponto 22l(a polyoxyether of alkyllated phenols blended with organic sulfonates) Test concentrations ranged from 0.1% downward to th'at at which 50% mortality was obtained. Each of the aqueous suspensons of the candidate compounds was sprayed onto the insects through the cloth netting by means of a hand-spray gun. Percent mortality in each case was recorded after 72 hours, and the LD-50 values, expressed as percent of toxicant in the aqueous spray, were recorded. These values are reported under the column GR in Table II.

For testing the Salt-marsh Caterpillar, test solutions were prepared in an identical manner and at concentrations the same as for the German Cockroach, above. Seetions of bitter dock. Rumex obtusifolus, leaves, 1l.5 inches in length were immersed in the test solutions for 1-0 to 15 seconds and placed on a wire screen to dry. The dried leaf was placed on a moistened piece of filter paper in a petri dish and infested with 5-3rd Instar larvae. Mortality of the larvae was recorded after 72 hours, and the LD-SO values are expressed as percent active ingredient in the aqueous suspension.

The Lygus Bug (LB), Lygus hesperus, was tested similarly as the German Cockroach. The caged insects were sprayed with the candidate compounds at concentrations ranging from 0.05% downward to that at which 50% mortality was obtained. After twenty-four and seventy-two hours, counts were made to determine living and dead insects. The LD'-50 (percent) values were calculated. These values are reported under the column LB in Table 11.

The insect species Black Bean Aphid (BA), Aphis fabae, (Scop.)was also employed in the test for insecticidal activity. Young nasturtium (Tropaeolum sp.) plants, approximately 2 to 3 inches tall, were used as the host plants for the Bean Aphid. The host plant was infested with approximately 50-75 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an emulsifying agent. The solution was applied as a spray to the infested plants. Concentrations ranged from 0.05 percent downward until an LD value was achieved. These results are given in Table II under the Column Roach germ ani ca ACARIOIDAL EVALUATION TEST The two-spoted mite (28M), Tetra nychus urticae (Koch), was employed in tests for miticides. Young pinto bean plants or lima bean plants (Phaseolus sp.) in the primary leaf stage were used as the host plants. The young pinto bean plants were infested with about 100 mites of various ages. Dispersions of candidate materials were prepared by dissolving 0.1 gram in ml. of a Liquid compositions are also useful and normally corm prise a dispersion of the toxicant in a liquid media, although it may be convenient to dissolve the toxicant directly in a solvent such as kerosene, fuel oil, xylene, akylated. naphthalenes or the like and use such organic suitable solvent, usually acetone. Aliquots of the toxicant 5 solutions directly. However, the more common procedure solutions were suspended in water containing 0.002% v./ is to employ dispersions of the toxicant in an aqueous v. Sponto 221, polyoxyethylene ether sorbitan monomedia and such compositions may be produced by formlaurate, an emulsifying agent, the amount of water being ing a concentrated solution of the toxicant in a suitable sufficient to give concentrations of active ingredient rang- 10 organic solvent followed by dispersion in water, usually ing from 0.05% to that at which 50% mortality was with the aid of surface active agents. The latter, which obtained. The test suspensions were then sprayed on the may be the anionic, cationic, or. nonionic types, are infested plants to the pointof run ofi. After seven days, exemplified by sodium stearate, potassium oleate and mortalities of post-embryonic and ovicidal forms were other alkaline metal soaps and detergents such as sodium determined. The percentage of kill was determined by lauryl sulfate, sodium naphthalene sulfonate, sodium comparison with control plant which had not been alkyl naphthalene, sulfonate, methyl cellulose, fatty alsprayed with the candidate compounds. The LD-50 cohol ethers, polyglycol fatty acid esters and other polyvalues were calculated using well-known procedures. oxyethylene surface active agents. The proportion of These values are reported under the columns 2SM- these agents commonly comprises l15% by weight of PE and ZSM-Eggs in Table II. the pesticidal compositions although the proportion is SYSTEMIC EVALUATION TEST gttiltiafigirlical and may be varied to suit any particular This test evaluates the root absorption and upward I i translocation of the candidate systemic compound. The 1 A process fo controlling insects comprising applytwo-Spotted mite telranychll-s "rtime, and 25 ing thereto an insecticidally effective amount of a comthe Bean Aphid (BA)Aphis fabae (Scop.) were empound h i h f ula ployed in the test for systemic acivity.

Young pinto bean plants in the primary leaf stage were used as host plants for the two-spotted mite. The pinto bean R S SCHFRa plants were placed in bottles containing 200 ml. of the test solution and held in place with cotton plugs. Only the roots were immersed. The test solutions were pre- 2 pared by dissolving the compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded about 1%. The toxicants were initially tested at a concentration of 10 parts per million (p.p.m.). Imin which R is alkyl having 1 to 4 carbon atoms; R is mediately after the host plant was placed in the test hydrogen, nitro or halogen; R is alkyl having 1 to 4 solution it was infested with the test species. Mortalities carbon atoms, and R is (l) ethynyl, (2) lower alkylwere determined after seven days. thio having 1 to 2 carbon atoms, or (3) cyano.

Young nasturtium plants were used as the host plants 2. The process of claim 1 in which R is methyl, R for the bean aphid. The host plants were transplanted is hydrogen, R is alkyl having 1 to 2 carbon atoms and into one pound of soil that had been treated with the R is lower alkylthio having 1 to 2 carbon atoms. candidate compound. Immediately after planting in the 3. The process of claim 1 in which R is methyl, R treated soil the plants were infested with aphids. Con- 5 is 4-chloro, R is alkyl having 1 to 2 carbon atoms and centrations of toxicant in the soil ranged from 10 ppm. R is lower alkylthio having 1 to 2 carbon atoms. per pound of soil downward until an L-D value was 4. The process of claim 1 in which R is methyl, R obtained. Mortality was recorded after 72 hours. is 4-chloro, R is alkyl having 1 to 2 carbon atoms and The percentage of kill of each test species was de- R is cyano. termined by comparison with control plants placed in 50 5. The process of claim 1 in which R is methyl, R distilled water or untreated soil. The LD-SO values were is 4-chloro, R is alkyl having 1 to 2 carbon atoms and calculated. These systemic test results are reported in R is ethynyl.

Table II under the columns BA-Sys and ZSM-Sys. 6. A process for controlling acarids comprising apply- TABLE IL-LD VALUES Compound HF, GR LB SMC BA, BA-Sys, PE, Eggs, Sys number g. percent percenf percent percent p.p.m. percent, percent ppm:

20 .1 .03 .1 .03 10 20 .1 .05 .1 .03 10 23 .1 .05 .1 .03 10 35 .1 .05 .1 .0a 30 .1 05 .1 .05 100 .1 .05 a0 .1 .05 .1 .03 10.0 40 .1 .05 .1 .05 30 .1 .05 .1 .05 10 .1 .05 .1 .03 100 s0 .1 .05 .1 .03 10.0 30 .1 .05 .1 .03 10.0

As those in the art are well aware, various techniques ing thereto an acan'cidally eifective amount of a comare available for incorporating the active component or pound having the formula toxicant in suitable pesticidal compositions. Thus, the pesticidal compositions can be conveniently prepared in s the form of liquid or solids, the latter preferably as 1 C=N Q P homogeneous free-flowing dusts commonly formulated by admixing the active component with finely divided solids or carriers as exemplified by talc, natural clays, diatomaceous earth, various flours, such as walnut shell, in which R is alkyl having 1 to 4 carbon atoms; R is sheat, soya bean, cottonseed and so forth. 7 hydrogen, nitro or halogen; R is alkyl having 1 to 4 carbon atoms, and R is (1) ethynyl, (2) lower alkylthio having 1 to 2 carbon atoms, or (3) cyano.

7. The process of claim 6 in which R is methyl, R is hydrogen, R is alkyl having 1 to 2 carbon atoms and R is lower alkylthio having 1 to 2 carbon atoms.

8. The process of claim 6 in which R is methyl, R is 4-chloro, R is alkyl having 1 to 2 carbon atoms and R is lower alkylthio having 1 to 2 carbon atoms.

9. The process of claim 6in which R is methyl, R is 4-chloro, R is alkylhaving l to 2 carbon atoms and R is cyano.

10. The process of claim 6 in which R is methyl, R is 4-ch1oro, R is alkyl having 1 to 2 carbon atoms and R is ethynyl.

8 References Cited UNITED STATES PATENTS 2,957,016 10/1960 Diamond 260944 X OTHER REFERENCES Hubele South African Patent Journal, vol. 2, No. 2, Feb. 26, 1969. 1 a

U.S. Cl. X.R. 424211 

